Catalyst system for the polymerization of olefins

ABSTRACT

Catalyst system for the polymerization of olefins consisting of (1) a powdered inorganic carrier and, applied thereto, (2) an active composition consisting of (2.1) a titanium, zirconium or vanadium compound and (2.2) an aluminum, magnesium or zinc compound. The characterizing feature is that the carrier (1) has been obtained by heating a substance of the general formula

United States Patent Trieschmann et al.

CATALYST SYSTEM FOR THE POLYMERIZATION OF OLEFINS Inventors: Hans-GeorgTrieschmann,

Hambach; Friedrich Urban, Limburgerhof; Guenther Schweier; Josef Kohnle,both of Ludwigshafen, all of Germany Badische Anilin- & Soda-FabrikAppl. No.: 153,832

[52] US. Cl. 252/429 C, 260/949 D [51] Int. Cl. C08f 1/40 [58] Field ofSearch 252/429 A, 429 C, 252/428 [56] References Cited UNITED STATESPATENTS 2,989,516 6/1961 Schneider 252/429 C X 3,008,943 11/1961 Guyer252/429 C X 3,168,484 2/1965 Engel et al 252/429 A 3,216,982 11/1965Orzechowski et al. 252/429 A X 3,288,720 11/1966 Moretti et al 252/429 A10/1970 Dassesse et a1. .7 252/429 C X 7/1971 Delbouille et al. 252/429A Primary ExaminerPatrick P. Garvin Attorney-Johnston, Root, OKeefe,Keil, Thompson & Shurtleff [5 7 ABSTRACT Catalyst system for thepolymerization of olefins consisting of (1) a powdered inorganic carrierand, applied thereto, (2) an active composition consisting of (2.1) atitanium, zirconium or vanadium compound and (2.2) an aluminum,magnesium or zinc compound. The characterizing feature is that thecarrier (1) has been obtained by heating a substance of the generalformula 'LI'( )0'(CQ;) '(H2O) in which Me denotes a metal or transitionmetal present in a divalent form; Me denotes a metal or transition metalpresent in a trivalent form; m is one of the integers 1 to 10; n is oneof the integers 2 to 5; o is one of the integers 2 to 24; p is one ofthe integers l to 3; and q is one of the integers 0 to 10; provided that2xm 3xn o 2xp an integer from 8 to 26 inclusive.

1 Claim, N0 Drawings CATALYST SYSTEM FOR THE POLYMERIZATION F OLEFINSThe present invention relates to a-catalyst system for thepolymerization of olefins, consisting of (1) a powdered inorganiccarrier having a particle diameter of from 0.1 to 2,000 1. andcontaining chemically combined metals, and (2) a Ziegler-type catalystapplied to said carrier and consisting of (2.1) a component selectedfrom the group consisting of chlorides, oxychlorides andalkoxy-chlorides of titanium, zirconium and vanadium, and (2.2) acomponent selected from the.

group consisting of saturated metal alkyls, saturated metal alkoxyalkylsand saturated metal alkyl halides of the metals aluminum, magnesium andzinc, provided that the ratio of carrier (1 is catalyst component (2.]based on the .transition metal is in the range 100:0.1 to 100:10 andthat the ratio of the transition metal in catalyst component (2.1 to themetal in catalyst component (2.2) is in tbe range 100:1 to 100:10,000.

It is known that catalyst systems of this kind have certain advantagesover comparable catalyst systems of other kinds; but disadvantages are(a) that the catalyst systems are not efficient to the desired extent,i.e., they are not capable of providing the desired quantity of olefinpolymer per unit weight of catalyst system, and (b) that the catalystsystems do not permit satisfactory control of the molecular weight ofthe olefin polymers by using hydrogen during polymerization.

It is an object of the invention to provide a catalyst system of thetype defined above, which suffers from the aforementioned disadvantageseither not at all or to a greatly reduced extent. I

We have found that the above object is achieved if the catalyst systemis based on a specific novel carrier.

The present invention thus relates to a catalyst system for thepolymerization of olefins consisting of 1) a powdered inorganic carrierhaving a particle diameter of from 0.1 to 2,000 ,u and preferably from0.1 to 1,000 p. and containing chemically combined metals and (2) aZiegler-type catalyst applied to said carrier.

and consisting of (2.1) a catalyst component selected from the groupconsisting of chlorides, oxychlorides and alkoxychlorides (in particularC, to C alkoxychlorides) of titanium, zirconium and vanadium, and (2.2)a catalyst component selected from the group consisting of saturatedmetal alkyls (in particular metal C, to C alkyls), saturated metalalkoxyalkyls (in particular metal C, to C alkoxy C, to C alkyls) andsaturated metal alkylhalides (in particular metal C, to C, alkylhalides)of the metals aluminum, magnesium and zinc, provided that the weightratio of carrier ('1) to catalyst component (2.1.), based on thetransition metal, is in the range 10020.1 to 100:10, preferably 100:0.3to 100:5, and that the atomic ratio of the transition metal in catalystcomponent (2.1 to the metal in catalyst component (2.2) is in the range100:1 to 100:l0,000', preferably 100210 to 100:6,000. The catalystsystem of the invention is characterized in that the carrier has beenobtained by heating a substance of the general formula:

for from 1 to 100 hours and preferably from 2 to 50 hours at atemperature of from 150 to 600 C and preferably from 250 to 400 C, inwhich formula Me" stands for a metal or transition metal present in adivalent form;

Me' stands for a metal or transition metal present in a trivalent form;

m is one of the integers 1 to 10 and preferably one of the integers 2 to8 and more preferably 6;

n is one of the integers 2 to 5 and preferably one of the integers 2 to4 and more preferably 2;

o is one of the integers 2 to 24 and preferably one of the integers 8 to18 and more preferably 16;

p is one of the integers 1 to 3 and preferably 1 or 2 and morepreferably 1;

q is one of the integers 0 to 10 and preferably one of the integers 2 to6 and more preferably 4;

provided that the following relationship holds: 2 m 3 n o 2 X p aninteger of from 8 to 26, preferably from 16 to 26 and more preferably18.

This catalyst system not only enables a desirably large quantity ofolefin polymer to be produced per unit weight of catalyst system butalso permits adequate control of the molecular weight of the olefinpolymers by the use of hydrogen during the polymerization process.

The following details may be given regarding the substances contained inthe catalyst system of the invention:

(1) the carrier (1) is obtained by'heating a compound of the specifiedgeneral formula for the specified period at the specified temperature.This may be effected, for example, simply be heating the particularcompound in an oven in the manner commonly used for drying inorganiccompounds containing water of crystallization. The desired particle sizemay be obtained in a simple manner, for example by milling.

In the said compound, suitable metals or transition metals (Me") presentin a divalent form are, for example, beryllium, magnesium, calcium,strontium, barium, manganese, iron, cobalt, nickel, palladium, platinum,copper, zinc, cadmium and mercury. Of these, particularly suitablemetals are magnesium, manganese, cobalt, nickel, copper, zinc andcadmium; particularly preferred metals being magnesium, manganese,cobalt, nickel, copper and zinc. The metals or transition metals (Me")may be present as single metals or as mixtures of two or more metals.

Suitable metals or transition metals (Me') present in a trivalent formare, for example, chromium, molybdenum, tungsten, iron, ruthenium,osmium, rhenium, iridium, aluminum and gallium. Of these, chromium,molybdenum, tungsten, iron and aluminum are particularly suitable,chromium and aluminum being preferred. The metals or transition metals(Me'") may be present as single metals or as mixtures of two or moremetals.

The compounds of the specified general formula are readily obtainable.One successful method of producing them is as follows: the selectedmetals or transition metals are used in the form of their water-solublesalts, such as chlorides, sulfates or, preferably, nitrates, and aredissolved together in water in a ratio which corresponds to the desiredcomposition of the compound and stoichiometrically obeys the specifiedgeneral formula. The resulting salt solution should contain a total ofabout 0.5 to 5 percent and preferably from 1.0 to 4 percent molar ofmetal ions or transition metal ions. It is heated to a temperature offrom 50 to 100 C and preferably from 60 to C and then combined, overfrom 0.5 to 120 minutes and preferably from 1 to 60 minutes, with anequivalent amount or, preferably, a slight excess of a lpercent andpreferably 1.5-4 percent molar aqueous solution of an alkalibicarbonate, in particular sodium bicarbonate, which has been heated atfrom 50 to 100 C and preferably from 60 to 90 C. We prefer to use anexcess of alkali bicarbonate, this being up to 20 percent and preferablyfrom 0.5 to 3 percent by weight, over the theoretical amount ofbicarbonate. On completion of the addition of alkali bicarbonatesolution, the mixture is conveniently stirred for about from to 30minutes and preferably from to minutes before the resulting precipitateis filtered off, washed with water and freed from excess water bysuction. In this manner, the compounds of the type under considerationare obtained in approximately quantitative yields. The manufacture ofthese compounds does not form part of the present invention.

(2) The active portion (2) of the catalyst and the catalyst components(2.1) and (2.2) are known and may be referred to as those commonly usedin the art.

(2.1) Suitable catalyst components of this'type are, for example, TiClZrCl.,, VCl VOCI TiCl (OC H and TiCl (OC 1-l,,) Of these, TiCl VCl, andVOCl are particularly suitable, TiCl, being especially preferred. Thecatalyst components (2.1) may be present as individual components or asmixtures of two or more components.

(2.2) Suitable catalyst components of this type are, for example, Mg(C HAl(C H AI(C H K J- m. K u nh. A](C12H25)3 2 5)2 Al(C H (OC H and Zn(C HOfthese Al(C H 3 1)3, 4 9)3: 11)a. 1z 2.-.)a. Al(C H Cl and Zn(C H areparticularly suitable, the aluminum compounds being preferred. Thecatalyst components (2.2) may be present as individual components or asmixtures of two or more components.

Application of the catalyst (2) to the carrier (1 may be carried out inconventional manner. For example, one method is to contact the carrierwith the active component (2.1) and subsequently with the activecomponent (2.2). More specifically, for example, the carrier may beconveniently left for several hours in boiling catalyst component (2.1)or a boiling solution of said catalyst component, under atmosphericconditions, and then thoroughly washed with an inert solvent and dried,for example in a vacuum. The resulting preliminary form of the catalystsystem may be very readily converted to the active form by combining itwith catalyst component (2.2), which may be present, for example, in asolution. This may take place in the vessel used for polymerization orin a separate vessel. Alternatively, the catalyst component (2.2) may beapplied to the carrier (1), followed by the catalyst component (2.1 Afurther possibility, for special cases, is to apply catalyst components(2.1) and (2.2) to the carrier simultaneously.

The catalyst system of the invention is particularly suitable for use inthe polymerization of C to C olefins, for example ethylene, propylene,butene, hexene and butadiene. Mixtures of olefins may also bepolymerized with the aid of the present system. The system isparticularly suitable for the polymerization of ethylene and propylene,and its beneficial properties are best revealed in the polymerization ofethylene.

The present invention does not relate to any particular process for thepolymerization of olefins with the aid of the catalyst system of theinvention. The polymerization of olefins using this system may becarried out in any conventional manner.

In the following Examples, the application of the catalyst (2) or itscomponents (2.1) and (2.2) to the carrier is carried out, as usual,under a blanket of inert gas (in this case nitrogen).

EXAMPLE 1 300 g of a material of the formula:

are placed in a drying oven and spread over an area of 400 cm and heldat a temperature of 320 C for 20 hours. This produces a carrier (1)which is then ground to a particle size of from about 5 to p.

A convertional extraction apparatus is taken, this being equipped with abulb, an extraction chamber fitted with a glass frit and disposed abovethe bulb, a stirrer located within the extraction chamber and a refluxcondenser fitted above the extraction chamber. 200 g of the carrier arecharged to the extraction chamber and 1.5 l of TiCL, are placed in thebulb. The TiCl, is then heated to the boil and held at the boil for afurther 7 hours, during which period, therefore, the carrier iscontacted by TiCl, vapor. The TiCl -laden carrier is then washed withn-heptane and dried in vacuo at ambient temperature. There is thusproduced a catalyst intermediate in which the ratio of carrier to TiCl,by weight, based on Ti, is about 100:1 100 g of this intermediate areplaced in a solution of 23 g of Al(C 1-l in 100 ml of n-heptane andstirred therein for 1 hour. The solvent is removed at ambienttemperature in vacuo. In the resulting catalyst system, the atomic ratioof Ti to Al is about 100:1,000. Using this system, olefins and inparticular ethylene may be polymerized with very good results.

EXAMPLES 2 TO 15 Each Example is a repetition of Example 1 except forthe modifications shown in the Table below. The first column of theTable gives the number of the Example, the second column gives theformula of the starting material used for the carrier, the third column(t) gives the time in hours during which the said starting material isheated, and the fourth column (T) gives the temperature at which thestarting material is heated in C.

The resulting catalyst systems are very suitable for use in thepolymerization of olefins, particularly ethylene and propylene. Theratio by weight of carrier to TiCl based on Ti, and the atomic ratio ofTi to A1 are, in each case, within the specified limits.

EXAMPLE 16 500 g of a material of the formula are placed in a dryingoven, spread over an area of 600 cm and heated at a temperature of 320 Cfor 24 hours. There is thus obtained a carrier (1) which is ground to aparticle size of from about to 200 [.L.

300 g of this carrier are immersed in l l of VOCl for 2 hours at atemperature of about 130 C (i.e., under reflux conditions), and theexcess VOCl is then decanted. This operation is repeated 3 times, eachtime with fresh VOCI and the product is then washed with n-hexane anddried in vacuo. There is thus obtained a catalyst intermediate in whichthe ratio of carrier to VOCI based on V, is 10024.1 by weight. 100 g ofthis intermediate are placed in a solution of 68.4 g of Al(C l-l in 100ml of n-heptane and stirred therein for 1 hour. The solvent is thenremoved in vacuo at ambient temperature. In the resulting catalystsystem, the atomic ratio ofV to Al is about 100:500. Using this system,olefins and in particular ethylene may be polymerized with very goodresults.

We claim:

1. A catalyst system for the polymerization of ethylene consisting of la powdered inorganic carrier having a particle diameter of from 0.1 to2,000 y. and containing chemically combined metals and (2) a Zieglertypecatalyst applied to said carrier and consisting of (2.1) titaniumtetra-chloride, and (2.2) a saturated aluminum alkyl, the alkyl grouphaving 1 to 12 carbon atoms, provided that the ratio of carrier (1) tocatalyst component (2.1 based on the titanium, is in the range UNITEDSTATES PATENT OFFICE" CERTIFICATE OF CORRECTION Patent No. 3,773,688Dated November 20, 1973 lnven ofl Hans-Georg Trieschmann et al It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

First pa e, left-hand column, thirteenth line, insert [30 ForeignApplication Priority Data June 27, 1970 Germany Q P 20 31 925-.8

First page, right-hand column, twenty-fifth line, "2m 3xn" should read2m 32cm Colunm l, line l9, "tbe"s hou1d read the Column 2, line -go,"be" should read by I Column 2, line 31, "the" should read the Column 2,line 58, "tbe" should read the Y Column. 3, line "the" should read the YColumn 3, line 63, "the" should read the Column A, line "29, "with"should read with 4 Column 4, line 32, insert after "100:1" 7

Column 6, line 15, insert after "1oo=1o,o0o"

Signed and sealed this 31st day of December 1974.

(SEAL) Attest McCOY M. GIBSON JR (3 MAPS? I I I n z L "n A I- LArresting Officer Commissioner of'Patents R M050 uscoMM-Dc 60376-P6911.5, GOVERNMENT PRINTING OFFICE: 19.9 0-856-33l,

